Visible-Light Photocatalytic Remote Halo-difluoroalkylation of Thioalkynes

doi:10.6023/cjoc202005066

Chinese Journal of Organic Chemistry ›› 2020, Vol. 40 ›› Issue (10): 3410-3419.DOI: 10.6023/cjoc202005066 Previous Articles Next Articles

Special Issue: 有机光催化虚拟合辑；黄乃正院士七十华诞专辑

可见光催化炔硫醚的远程卤-二氟烷基化反应

朱海倩^a, 商甜波^a, 卢增辉^b, 罗芳^a, 朱钢国^a

a 浙江师范大学化学系先进催化材料教育部重点实验室浙江金华 321004;
b 万州区生态环境监测站重庆 404000

收稿日期:2020-05-24 修回日期:2020-06-06 发布日期:2020-06-13
通讯作者: 朱钢国 E-mail:gangguo@zjnu.cn
基金资助:
国家自然科学基金（No.21672191）、浙江省自然科学基金（No.LZ20B020002）和浙江省教育厅（No.Y201942955）资助项目.

Visible-Light Photocatalytic Remote Halo-difluoroalkylation of Thioalkynes

Zhu Haiqian^a, Shang Tianbo^a, Lu Zenghui^b, Luo Fang^a, Zhu Gangguo^a

a Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Department of Chemistry, Zhejiang Normal University, Jinhua, Zhejiang 321004;
b Wanzhou Ecological Environment Monitoring Station, Chongqing 404000

Received:2020-05-24 Revised:2020-06-06 Published:2020-06-13
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21672191), the Natural Science Foundation of Zhejiang Province (No. LZ20B020002) and the Education Department of Zhejiang Province (No. Y201942955).

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Abstract

Fluoroalkylated alkenes are of significant importance in life sciences and functional materials. The fluoroalkylation of alkynes offers an efficient method for the synthesis of functionalized fluoroalkylated alkenes. However, the current methods are often limited to 1,2-difunctionalization, while the remote fluoroalkylative difunctionalization of alkynes has been rarely developed. Herein, a novel visible-light-induced remote halo-difluoroalkylation of thioalkynes is realized with difluoroalkyl halides as the radical source, forming distally halogenated (Z)-fluoroalkylated alkenes in moderate to high yields with excellent regio-, stereo-, and site-selectivity. The notable features of this reaction include the mild reaction conditions, broad substrate scope, concurrent formation of three new chemical bonds, and a thermodynamically less stable (Z)-alkene, thus enabling it a highly attractive method for organic synthesis. It represents a new advance on the direct C-H bond halogenation. Preliminary mechanistic studies indicate a cascade radical process involving the heteroatom-induced β-fluoroalkylation of C-C triple bonds, intramolecular 1,5-hydrogen atom transfer (1,5-HAT), single electron transfer (SET) oxidation and halide addition.

Key words: difluoroalkyl, visible-light photoredox catalysis, thioalkyne, C-H halogenation, radical, selectivity

Cite this article

Zhu Haiqian, Shang Tianbo, Lu Zenghui, Luo Fang, Zhu Gangguo. Visible-Light Photocatalytic Remote Halo-difluoroalkylation of Thioalkynes[J]. Chinese Journal of Organic Chemistry, 2020, 40(10): 3410-3419.

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References

[1] For selected reviews, see:(a) Purser, S.; Moore, P. R. Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320.
(b) O'Hagan, D. Chem. Soc. Rev. 2008, 37, 308.
[2] (a) Burke, T. R.; Lee, K. Acc. Chem. Res. 2003, 36, 426.
(b) Meanwell, N. A. J. Med. Chem. 2011, 54, 2529.
(c) An, L.; Tong, F.; Zhang, X. Acta Chim. Sinica 2018, 76, 977(in Chinese). (安伦, 童非非, 张新刚, 化学学报, 2018, 76, 977.)
(d) Tao, X.; Sheng, R.; Bao, K.; Wang, Y.; Jin, Y. Chin. J. Org. Chem. 2019, 39, 2726(in Chinese). (陶雪芬, 盛荣, 鲍堃, 王玉新, 金银秀, 有机化学, 2019, 39, 2726.)
(e) Dai, J.; Lei, W.; Liu, Q. Acta Chim. Sinica 2019, 77, 911(in Chinese). (戴建玲, 雷文龙, 刘强, 化学学报, 2019, 77, 911.)
[3] (a) Long, Z.-Y.; Chen, Q.-Y. J. Org. Chem. 1999, 64, 4775.
(b) Huang, X.-T.; Chen, Q.-Y. J. Org. Chem. 2001, 66, 4651.
(c) Ke, M.; Feng, Q.; Yang, K.; Song, Q. Org. Chem. Front. 2016, 3, 150.
(d) Feng, X.; Wang, X.; Chen, H.; Tang, X.; Guo, M.; Zhao, W.; Wang, G. Org. Biomol. Chem. 2018, 16, 2841.
(e) Li, K.-K.; Zhang, X.-X.; Chen, J.-C.; Gang, Y.; Yang, C.-H.; Zhang, K.-Y.; Zhou, Y.-Y.; Fan, B.-M. Org. Lett. 2019, 21, 9914.
[4] (a) He, Y.-T.; Wang, Q.; Li, L.-H.; Liu, X.-Y.; Xu, P.-F.; Liang, Y.-M. Org. Lett. 2015, 17, 5188.
(b) He, Y.-T.; Li, L.-H.; Wang, Q.; Wu, W.; Liang, Y.-M. Org. Lett. 2016, 18, 5158.
(c) Wang, Q.; Zheng, L.; He, Y.-T.; Liang, Y.-M. Chem. Commun. 2017, 53, 2814.
(d) Zhang, Y.; Zhang, J.; Hu, B.; Ji, M.; Ye, S.; Zhu, G. Org. Lett. 2018, 20, 2988.
(e) Liang, J.-Q.; Huang, G.-Z; Peng, P.; Zhang, T.-Y.; Wu, J.-J.; Wu, F.-H. Adv. Synth. Catal. 2018, 360, 2221.
[5] Zhang, B.-S.; Gao, L.-Y.; Zhang, Z.; Wen, Y.-H.; Liang, Y.-M. Chem. Commun. 2018, 54, 1185.
[6] Xiang, Y.; Li, Y.; Kuang, Y.; Wu, J. Chem.-Eur. J. 2017, 23, 1032.
[7] (a) Wang, S.; Zhang, J.; Kong, L.; Tan, Z.; Bai, Y.; Zhu, G. Org. Lett. 2018, 20, 5631.
(b) Guo, W.-H.; Zhao, H.-Y.; Luo, Z.-J.; Zhang, S.; Zhang, X. ACS Catal. 2019, 9, 38.
[8] Li, Y.; Li, H.; Hu, J. Tetrahedron 2009, 65, 478.
[9] Xu, T.; Cheung, C. W.; Hu, X. Angew. Chem., Int. Ed. 2014, 53, 4910.
[10] Zhong, J.-J.; Yang, C.; Chang, X.-Y.; Zou, C.; Lu, W.; Che, C.-M. Chem. Commun. 2017, 53, 8948.
[11] Li, G.; Cao, Y.-X.; Luo, C.-G.; Su, Y.-M.; Li, Y.; Lan, Q.; Wang, X.-S. Org. Lett. 2016, 18, 4806.
[12] Wu, G.; von Wangelin, A. J. V. Chem. Sci. 2018, 9, 1795.
[13] Shang, T.; Zhang, J.; Zhang, Y.; Zhang, F.; Li, X.-S.; Zhu, G. Org. Lett. 2020, 22, 3667.
[14] Xiong, Z.; Zhang, F.; Yu, Y.; Tan, Z.; Zhu, G. Org. Lett. 2020, 22, 4088.
[15] For selected reviews on photocatalysis, see:(a) Narayanam, J. M. R.; Stephenson, C. R. J. Chem. Soc. Rev. 2011, 40, 102.
(b) Xuan, J.; Xiao, W.-J. Angew. Chem., Int. Ed. 2012, 51, 6828.
(c) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322.
(d) Matsui, J. K.; Lang, S. B.; Heitz, D. R.; Molander, G. A. ACS Catal. 2017, 7, 2563.
[16] For selected reports on remote C-H halogention, see:(a) Kundu, R.; Ball, Z. T. Org. Lett. 2010, 12, 2460.
(b) Liu, T.; Myers, M. C.; Yu, J.-Q. Angew. Chem., Int. Ed. 2017, 56, 306.
(c) Herron, A. N.; Liu, D.; Xia, G.; Yu, J.-Q. J. Am. Chem. Soc. 2020, 142, 2766.
(d) Short, M. A.; Blackburn, J. M.; Roizen, J. L. Angew. Chem., Int. Ed. 2018, 57, 296.
[17] (a) Yang, Z.; Chen, X.; Kong, W.; Xia, S.; Zheng, R.; Luo, F.; Zhu, G. Org. Biomol. Chem. 2013, 11, 2175.
(b) Zhu, G.; Kong, W.; Feng, H.; Qian, Z. J. Org. Chem. 2014, 79, 1786.
[18] Nie, X.; Cheng, C.; Zhu, G. Angew. Chem., Int. Ed. 2017, 56, 1898.
[19] (a) Jin, W.; Wu, M.; Xiong, Z.; Zhu, G. Chem. Commun. 2018, 54, 7924.
(b) Wan, Y.; Shang, T.; Lu, Z.; Zhu, G. Org. Lett. 2019, 21, 4187.
[20] For selected reports on HAT of vinyl radicals, see:(a) Curran, D. P.; Shen, W. J. Am. Chem. Soc. 1993, 115, 6051.
(b) Bogen, S.; Malacria, M. J. Am. Chem. Soc. 1996, 118, 3992.
(c) Hu, M.; Fan, J.-H.; Liu, Y.; Ouyang, X.-H.; Song, R.-J.; Li, J.-H. Angew. Chem., Int. Ed. 2015, 54, 9577.
(d) Qiu, J.-K.; Jiang, B.; Zhu, Y.-L.; Hao, W.-J.; Wang, D.-C.; Sun, J.; Wei, P.; Tu, S.-J.; Li, G. J. Am. Chem. Soc. 2015, 137, 8928.
(e) Huang, L.; Ye, L.; Li, X.-H.; Li, Z.-L.; Lin, J.-S.; Liu, X.-Y. Org. Lett. 2016, 18, 5284.
(f) Gloor, C. S.; Dénès, F.; Renaud, P. Angew. Chem., Int. Ed. 2017, 56, 13329.
(g) An, X.-D.; Jiao, Y.-Y.; Zhang, H.; Gao, Y.; Yu, S. Org. Lett. 2018, 20, 401.
(h) Ratushnyy, M.; Parasram, M.; Wang, Y.; Gevorgyan, V. Angew. Chem., Int. Ed. 2018, 57, 2712.
(i) Wu, S.; Wu, X.; Wang, D.; Zhu, C. Angew. Chem., Int. Ed. 2019, 58, 1499.
(j) Yang, S.; Wu, X.; Wu, S.; Zhu, C. Org. Lett. 2019, 21, 4837.
(k) Liu, T.; Qu, C.; Xie, J.; Zhu, C. Chin. J. Org. Chem. 2019, 39, 1613(in Chinese). (刘涛, 屈川华, 谢劲, 朱成建, 有机化学, 2019, 39, 1613.)
(l) Li, H.; Guo, L.; Feng, X.; Huo, L.; Zhu, S.; Chu, L. Chem. Sci. 2020, 11, 4904.
(m) Wu, S.; Wu, X.; Wu, Z.; Zhu, C. Sci. China: Chem. 2019, 62, 1507.

可见光催化炔硫醚的远程卤-二氟烷基化反应

Visible-Light Photocatalytic Remote Halo-difluoroalkylation of Thioalkynes

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